N-(1-azido-2 2 2-trihaloethyl) azides and carbamates

ABSTRACT

AZIDES OF THE FORMULA: R-NH-CH(-N3)-CX3 IN WHICH X IS CL OR BR AND R IS A CARBOXYACYL, SULFONYLACYL OR ALKOXYCARBONYL GROUP. THESE AZIDES ARE NEMATOCIDAL.

United States Ratent 3,636,062 N-(l-AZIDO-2,2,2-TRIHALOETHYL) AZIDES AND CARBAMATES Malcolm S. Singer, Point Richmond, Calif., assignor to Chevron Research Company, San Francisco, Calif. N Drawing. Filed Jan. 7, 1969, Ser. No. 789,595 Int. Cl. C07c 117/00; C07d 109/00 US. Cl. 260-349 Claims ABSTRACT OF THE DISCLOSURE Azides of the formula:

a R-NH-bH-CX,

in which X is Cl or Br and R is a carboxyacyl, sulfonylacyl or alkoxycarbonyl group. These azides are nematocidal.

FIELD OF INVENTION This invention concerns N-(l-azido-2,2,Z-trihaloethyl) amides and carbamates and their use as nematocides.

INVENTION DESCRIPTION The novel azides of this invention are carbamates, carboxamides and sulfonamides. These azides are of the formula.

wherein X is halogen of atomic number 17 to 35 and R is wherein Z is a chalcogen atom of atomic number 8 to 16 and R is hydrogen, nonarylhyclrocar-byl of l to carbon atoms which is free of acetylenic unsaturation, nonarylhalohydrocarbyl which is free of acetylenic unsaturation and of 1 to 10 carbon atoms and 1 to 3 halogen atoms of atomic number 17 to 35, monocarbocyclicaryl of 6 to carbon atoms, the benzene nucleus of said monocarbocyclicaryl radical being substituted with 0 to 3 alkoxy groups of 1 to 3 carbon atoms each, halogens of atomic number 17 to 35 or nitro groups, alkoxy of 1 to 6 carbon atoms, phenylthioalkyl in which the alkyl is of l to 3 carbon atoms and the phenyl is substituted with O to 2 halogen atoms of atomic number 17 to 35, phenylsulfonylalkyl in which the alkyl is of l to 3 carbon atoms and the phenyl is substituted with 0 to 2 halogen atoms of atomic number 17 to 35, or a S-membered heterocyclic radical of 4 nuclear carbon atoms, one of which is bound to the carbonyl radical of (a), and a single chalcogen heteroatom of atomic number 8 to 16, or

wherein R is a nonarylhydrocarbyl radical of 1 to 6 carbon atoms which is free of acetylenic unsaturation and is substituted with 0 to 2 halogen atoms of atomic number 17 to 35 or a monocarbocyclicaryl radical of 6 to 10 carbon atoms in which the benzene nucleus is substituted with 0 to 2 halogens of atomic number 17 to 35, nitro groups or methoxy groups. Halogens of atomic number 17 to 35 are chlorine and bromine. Chalcogen atoms of atomic number 8 to 16 are oxygen and sulfur. The term nonaryl as used herein refers to radicals in which a benzene nucleus is not present. Preferably X is chlorine and Z is oxygen in the above formulas.

Particularly preferred compounds represented by the above formula are those in which X is chlorine, Z is oxygen, R is hydrogen, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 3 carbon atoms, monoalkenyl of 2 to 5 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, monocarbocyclicaryl of 6 to 10 carbon atoms in which the benzene nucleus is substituted with 0 to 3 chlorine atoms, nitro groups or alkoxy groups of 1 to 2 carbon atoms each, chloroalkyl of 1 to 6 carbon atoms and 1 to 3 chlorine atoms, phenylthiomethyl in which the phenyl group is substituted with 0 to 2 chlorine atoms or phenylsulfonylmethyl wherein the phenyl group is substituted with 0 to 2 chlorine atoms and R is alkyl of 1 to 6 carbon atoms or phenyl substituted with 0 to 2 chlorine atoms.

Hydrocarbyl radicals which R represents in the above formula include alkyl, alkenyl, cycloalkyl and cycloalkenyl radicals. Specific examples of such radicals are methyl, ethyl, isopropyl, butyl, hexyl, heptyl, nonyl, decyl, vinyl, propenyl, butenyl, pentenyl, ocetenyl, decenyl, cyclopropyl, cyclobutyl, cyclohexyl, cyclooctyl, cyclohexenyl and cyclooctenyl. Corresponding halohydrocarbyl groups represented by R include chloromethyl, bromomethyl, 2,2-dichloroethyl, 3-bromo-2-chloropropyl, 2- bromoethyl, 5 chloro 2 pentenyl, 6-chlorohexyl, 9- bromodecyl, 4-brornocyclohexyl, 2,4,6-tribromocyclohexyl, 2-chlorocyclohexenyl and 3-chlorocyclobutyl.

Examples of monocarbocyclic aryl radicals which R may represent are phenyl, tolyl, xylyl, cumyl, p-butylphenyl, p-octylphenyl, 2,4-dibutylphenyl, cinnamyl, benzyl, p-methoxyphenyl, 2-methoxy-4-tolyl, 2,4,6-tripopoxyphenyl, 2,4,6-trinitrophenyl, 3,5-dibromophenyl, 2-chloro- 4-methoxyphenyl, 2-bromo-4-tolyl, 2-chloro 4 ethylphenyl, 2,4,6-tribromophenyl, 2,4-diethoxybenzyl, 2,4-dinitrophenyl, 2-chloro-5-nitrophenyl and 5-nitro-2-tolyl.

Alkoxy radicals which R may represent include methoxy, ethoxy, isopropoxy, butoxy, isopentoxy and hexoxy.

Heterocyclic radicals which R may represent include 2-furyl, 4-furyl, 5-nitro-2-furyl, 5-chloro-2-furyl, 4-bromo- 2-furyl, 3-thienyl, 5-nitro-2-thienyl, 4-chloro-2-thienyl, 5- bromo-3-thienyl and Z-thienyl.

Phenylthioalkyl groups represented by R are illustrated by phenylthiomethyl, phenylthioethyl, phenylthioisopropyl, 4-chlorophenylthioethyl, 2 chlorophenylthiopropyl, 3,5-dibromophenylthioethyl, 2,4-diehlorophenylthiomethyl and 2-chloro-4-bromophenylthiopropyl.

Phenylsulfonylalkyl radicals represented by R include phenylsulfonylmethyl, phenylsulfonylethyl, phenylsulfonylisopropyl, 4-chlorophenylsulfonylethyl, 2-chlorophenylsulfonylpropyl, 3,5-dibromophenylsulfonylethyl, 2,4-dichlorophenylsulfonylmethyl and 2-chloro-4-bromophenylsulfonylpropyl.

Nonarylhydrocarbyl radicals which R may represent include alkyl, alkenyl and cycloalkyl. Examples of such radicals are methyl, ethyl, propyl, amyl, heXyl, allyl, pentenyl, 2,2-dibromoethyl, chloroallyl, bromobutenyl, cyclopropyl, cyclobutyl, cyclohexyl, 4-chlorocyclohexyl, 2- bromocyclohexyl, 3,5-dichlorocyclohexyl, 3-br0mocyc1obutyl, chloromethyl, bromomethyl, 2,2-dichloropropyl and 6-chl0rohexyl. Aryl radicals represented by R include benzyl, phenyl, tolyl, xylyl, cumyl, 2,4-dinitrophenyl, 3,5- dimethoxyphenyl, 4-chlorobenzyl, 2-bromo-4-tolyl, 2- methoxyphenyl, 4chlorophenyl, 2-bromophenyl, 4-bromo- 2-chlorophenyl, 3,5-dichlorophenyl and 2,4-dibromophenyl.

Carboxamides represented by the above formula include N-( 1-azido-2,2,Z-trichloroethyl -2,4-dipropoxybenzamide,

N-( l-azido-2,2,Z-tribromoethyl -cyclohe xanecarboxamide,

N-( 1-azido-2,2,2-tribromoethyl) -formamide,

N l-azido-Z-bromo-2,2-dichloroethyl -thioformaniide,

N-( l-azido-2,2,2-trichloroethyl -3-chlorobutanarnide,

N 1-azido-2,2-dibromo-Z-chloroethyl -hexanamide,

N- I-azid-2-bromo-2,Z-dichloroe thyl) -4,5-dicl1lorohexanamide,

N-( 1-azido-2,2,2-trichloroethyl -2-bromoacetamide,

N-(1-azido-2,2,2-trichloroethyl)-thiobenzamide,

N-( l-azido-2,2,2-tribromoethyl -thioacetamide,

N-(1-azido-2-bromo-2,2-dichloroethyl)-3 -brornothiopropionamide,

N(1-azido-2,2,2-trichloroethyl)-thiocyclopropanecarboxamide,

N-( l-azido-2,2,2-trichloroethyl) -4-ethoxybenzamide,

N-( l-azido-2,2-dibromo-2'chloroetl1yl -2-chloro-4- bromothiobenzamide,

N-(1-azido-2,2,2-trichloroethyl)-4-bromo-3-nitrobenzamide,

N- l-azido-2,2,2-tribromoethyl -fu ramide,

N-( l-azido-2,2,2-trichloroethyl) -octanamide,

N-( l-azido-2,2,2-trichloroethyl) -decanamide,

N-( l-azido-2-bromo-2,2-dichl0roethyl -4-chlorocyclohexanecarboxamide,

N-(1-azido-2,2,2-trichloroethyl)-cinnam amide,

N-( l-azido-2,2,2-tribromoethyl -4-bromocinnamamide,

N- lazido-2,2,2-trichloroethyl S-hexeneamide,

N-( 1-azido-2,Z-dibromo-Z-chloroethyl --chlorofuramide,

N (1-azido-2,2,2-trichloroethyl)-2-phenylacetamide,

N-( l-azido-2,2,2-trichloroe thyl) -3- (4-chlorophenyl) propionamide,

N-( l-azido-2,2,Z-trichloroethyl -2- (4-bromophenylsulfonyl) acetamide,

N-( l -azido-2,2-dibromo 2-chloroethyl -5-nitrofuramide,

N( 1-azido-2-bromo-2,2-dichloroethyl -3- (2,4-dichlorophenylsulfonyl thiopropionamide,

N-( l-azido-2,2,2-trichloroethyl) -2-phenylthio-thioacetamide,

N-( 1-azido-2,2-dibromo-Z-chloroethyl -3 3,5 -dichl0ro phenylthio propionamide,

N-( l-azido-2,2,2-tribromoeth yl -4- 6-bromo-2-chlorophenylthio butanamide,

N-( l-azido-2,2,2-trichloroethyl -4- 3-bromophenylsulfonyl) butanamide,

N-(1-azido-2,2,Z-tribromoethyl)-4-phenylsulfonylthiobutanamide and N-(1-azido-2,2-dibromo-2-chloroethyl)-3,5-diethoxythiobenzamide.

Sulfonamides represented by the above formula include N-( l-azido-2,2,Z-trichloroethyl -4-bro mobenzenesulfonamide,

N-( 1-azido-2-bromo-2,Z-dichloroethyl) -3 ,4-dichlorobenzenesulfonamide,

N-(1-azido-2,2,2-trichl0r0ethyl)-3,S-dimethoxybenzeuesulfonamide,

N( 1-azido-2,2,2-trichloroethyl)-3-nitrobenzenesulfonamide, and

N-( l-azido-2-bromo-2,2-dichloroethyl) -2-nitro-4-cl1lorobeuzenesulfonarnide,

N-( 1-azido-2,2,2-trichloroethyl -methanesulfonamide,

N 1-azido2, 2,2-tribromoethyl) -e thanesulfonamide,

N-( l-azido-2,2,2-tribromoethyl propenesulfon amide,

N-( 1-azido-2-bromo-2,2-dichloroethyl hexanesulfonamide,

N-(1-azido-2,2,2-trichloroethyl)-2,2-dichloroethanesulfona mide,

N- l-azido-2,2,2-trichloroethyl -bromobutenesulfonamide,

N- 1-azido-2,Z-dibromo-2-cl1loroethyl hexenesulfonamide,

N- l-azido-2,2,2-trichloroethyl) cyclohexansulfonamide,

N-( l-azido-2,2,2-tribromoethyl cyclobutanesulfonamide,

N- (2-azido-2,2,2-trichloroethyl -3,5-dibromocyclohexanesulfonamide,

N-( l-azido-Z,2-dibromo-2-chloroethyl -3-chlorocyclobutanesulfonamide,

N-( 1-azido-2,2,2-trichloroethyl -4-chlorobutanesulfonamide and N-( l-azido-2,2,2-trichloroethyl -3 -brorno-4-chloropentanesulfonamide.

Carbamates represented by the above formula include N-(l azido 2 bromo 2,2 dichloroethyl) isopropylcarbamate, N-( l-azido 2,2,2 trichloroethyl) butylthiocarbarnate, N-(l azido 2,2,2 trichloroethyl) heXylcarbamate, N-(l-azido-2,2,2-trichloroethyl) methylthiocarbamate and N-(1-azido-2,2-dibromo 2 chloroethyl) ethylcarbarnate.

The azides of this invention are prepared by reacting a corresponding N-(1,2,2,2-tetrahaloethyl) amide with an alkali metal azide. This reaction proceeds according to the following equation:

wherein R and X are as defined previously and M is an alkali metal such as sodium, potassium and lithium. This reaction will normally be carried out in polar, aprotic solvents such as acetonitrile, dimethoxyethane, tetrahydrofuran, dimethylformamide and dimethylsulfoxide. Normally the N-(l-chloro-2,2,2-trihaloethyl)amide will be dissolved in the solvent to a concentration of about 5 and 20% by Weight and the solid alkali metal azide will be added with agitation. The temperature of this reaction will usually be in the range of ambient temperature up to about C. More usually it will be between about 20 C. and 60 C. Stoichiornetric proportions of the reactants will normally be employed. The pressure used in the reaction is not critical. For convenience atmospheric or autogenous pressure may be used. The N-(lazido-2,2,2-trihaloethyl)amide or carbamate product may be recovered from the reaction mixture by filtering out the alkali metal halide and stripping the solvent from the filtrate.

The organic starting materials for the above reaction may be prepared by the method of British Pat. No. 993,051. In this procedure an amide or a carbamate is condensed with a trihaloacetaldehyde. The resulting hydroxy compound is further reacted with thionyl chloride to replace this hydroxyl group with a chlorine atom. The reaction is as follows:

wherein R and X are as defined previously.

EXAMPLES The following examples illustrate the azides of this invention and their preparation. Unless otherwise indicated, percentages are by weight.

Calculated (percent): Cl, 39.0; S, 8.80. Found (percent): Ol, 37.82; S, 9.39.

Other azides of this invention were prepared using the general procedures described above. These azides are tabulated in Table I below.

TABLE I Element analysis, percent Melting Cl S point,

Compound 0 Calculated Found Calculated Found N (1-azido-2,2,2-trichloroethyl) 3,5-dimethoxybenzamide 03-99 30. 06 30. 35 N (l-azido-2,2,2-trichloroethyl)-3,4,5-trimetl1oxybenzarnide 125-127 27. 8 27. 65 N-(lazido-2,2,2-trichloroethyl)-piva1amide 63-57 38. 8 38. 80 N-(l-azido-2,2,2-trichloroethyl)-cyclopropane carboxamide 125-127 41. 4 40. 75 N-(1azido2,2,

plonamide 1 37-38 56. 4 52. 35 N-(1-azido-2,2,

acetamide 87-89 31. 4 31. 35 9. 43 9. 34 N-(1azido-2,2,2triehlor0ethyl)-acrylam 64437 41. 4 N-(l-azido-2,2,2-trichloroethy1)-fu.ramide. 94-98 37. 6 N-(1azide-2,2,2-triehl0roethyl)-3-ehloropropionamide 78-89 50. 7 N -(1-azido-2,2, trichloroethyl)-3,4-dichlorobenzamide 127-129 40. 0 N 1-azido-2,2,2-trichloroethyl) 4-chloro-3-nitrobenzamide 135-137 38.05 N-(1-azido 2,2,2-trichloroethyl)-2,4diohlorobenzamide A 81-83 49. 0 N -(1-azido-2,2,2-trichloroethyl)2-chlorobenzamide 110-l16 43. 3 N. (1-azido-2,2,2-trichl0r0ethyl)-2-(4-ch10r0phenylsultonyl) aeetamide 120-123 35. 0 N-(1-azido-2,2,2-triehloroet hyl) 2-phenylsultonyl.

acetamide Liquid 28. 63 28. 95 8. 62 8. 62 N-(1-azid0-2,2,2-trichloroethyl)-dichloroacetamide 1 8-110 59. 1 58. 10 N-(l-azido-2,2,2-trichloroethyl)-2-eh1oroacetamide 71. 5-72 5 53.4 52.36 N -(lazide-2,2,Z-trichloroethyl)-2-(4-chlorophenyl thio) aoetamide 74-76 37. 98 37. 85 8. 58 8. 55 N-(1-azid0 2,2,2-trichloroethyl)-isopropylcarbamate 3 46. 5-48. 5 38. 05 36. 95

N-eale., 17.80%; found, 16.70%.

2 Ncalc. 2105, found 21.00; C-cale. 18. 2, found 17.90.

3 Ncalc. 2 .34, found 17.75.

EXAMPLE 1 UTILITY 21.1 g. N-( l,2,2,2-tetrachloroethyl) formamide was dissolved in 100 ml. of acetonitrile. 6.5 g. of sodium azide was heated slowly at ambient temperature with stirring. The mixture was stirred overnight, after which the reaction mixture was filtered. The acetonitrile was removed from the filtrate leaving an organe liquid residue. This residue was cooled in an ice bath and the sides of the vessel containing the residue were scratched. After minutes of this treatment, about 11 g. of N-(l-azido- 2,2,2-trichloroethy1) formamide precipitated. This compound melted at 42-54 C. Its elemental analysis was:

Calculated (percent): Cl, 48.97; N, 25.75. Found (percent): Cl, 48.05; N, 25.50.

EXAMPLE 2 8.7 g. of N-(l,2,2,2-tetrachloroethyl)-4-chlorobenzenesulfonamide was dissolved in about ml. acetonitrile. To this solution 1.58 g. of sodium azide was added with mixing. The combined mixture was stirred for one hour. Reaction mixture was then filtrated and the solid was washed with cold acetonitrile. The acetonitrile was evaporated from the filtrate leaving an oil residue. This residue solidified upon standing overnight, giving 9.0 g. N-(l-, azido 2,2,2 trichloroethyl) 4 chlorobenzenesulfonamide. This sulfonamide melted at 112ll6 C. its element analysis was:

The azides of this invention exhibit excellent biological activity against nematodes. The nematocidal activity of representative azides of this invention are illustrated by testing them according to the following method.

A 0.38 ml. portion of a 3% acetone solution of the test compound was diluted with 1 ml. acetone. The resulting solution was homogeneously mixed with 20 cc. of vermiculite. The treated vermiculite was then mixed homogeneously with 750 g. of soil, dry weight basis, which was severely infested with nematodes (mixed culture of Meloidogyne javanica and Meloidogyne incognita). This mixing gave a concentration of approximately 15 parts of the test compound per million parts of soil. This treated soil was stored for 4 days at 6575 It was then divided equally into 3 parts, each of which was put into a separate pot and kept for another 3 days. A 3-week old tomato (v. Bonny Best) seedling was then transplated into each pot and incubated for 13 days under greenhouse conditions. After this period they were removed and the soil was washed from their roots. The nematocidal effectiveness of the test compound was determined by observing each plant for signs of nematode invasion (number of galls formed, stunting, etc.).

The results of these tests, reported as the average of the 3 replicates on a 0 to basis0 indicating no effectiveness; 100 indicating complete effectivenessare reported in Table II.

TABLE II Nemato cidal activity, Compound: percent N-(1-azido-2,2,2-trichloroethyl)-3, 5-

dimethoxybenzamide 100 N-( l-azido-Z, 2,2-triehloroethyl) -3 ,4 ,5-

trimethoxybenzamide 1 N-(1-azido-2, 2,2-triehloroethy1) pivalamide 100 N-(1-azido-2, 2, 2-trichloroethyl) eyclopropane carb oxamide 100 N-(1-azido-2,2, 2-trichloroethy1) -2,2-

diehloropropionamide 100 N-( l-azido-2, 2, 2-triehloroet-hyl) -2- phenylsufen ylaeetamide 35 N-(1-aziclo-2,2,2-trichloroethyl)- acrylamide 1 0O N-(1-azido2,2, 2-trichloroethyl) -furamide 1 00 N-(1-azido-2,2, 2-trichloroethyl) -3- chloropropionamide 99 N-(1-azid0-2, 2, 2-trichloroethyl) -3, 4-

diehlorobenzamide 93 N l-azido-2, 2, 2-trichloroethyl) -4-chloro- 3-nitrobenzamide 95 N-( l -azido-2,2,2-trichloroethyl) 2,4-

dichlorobenzamide 97 N-(1-azido-2,2, 2-trichloroethyl) -2- ehlorobenzamide 95 N(1-azido-2,2, 2-t-rieh1oroe thyl) -2-(4- chloro phenylsulfonyl) acetamide 100 N- l-azido-2, 2, 2-trichloroethyl) -2- phenylsulfonylacetamide 100 N- l-azid 0-2, 2, 2-trich1oroe thyl) -2-ehloro- 5-nitrobenzamide 93 N-( l-azido-Z, 2, 2-trichloroethyl) dichloroaeetamide 1 00 N- l-azido-2,2, 2-trichloroethyl) 2- chloroacetamide 100 N-( l-azido-2, 2 2-trichloroethyl) -2-(4- chlorophenylthio) -aceta-rnide 96 N-( l-azido-Z, 2,2-trichloroethyl) isopropylcarb amate 100 N-( l-azido-Z, 2, Z-trichloroe thyl) -4- chlorobenzenesulfonamide 100 As illustrated above, the azides of this invention may be used to control plant-parasitic nematodes by exposing them to a toxic amount of the azide. Thus, these azides will normally be applied to nematode-infested soil at dosages in the range of 3 to 40 lbs. per acre. They may be applied as liquid formulations by spraying or injection. They may also be applied as solid formulations containing carriers such as soil, sawdust, clay and the like. When used as a solid, these azides will usually be plowed into the soil to facilitate their contact with the nematodes. Following their application to the soil, the soil 'will be watered to disperse the azide below ground level.

The above-mentioned liquid formulations will comprise one or more azides admixed with a suitable solvent or diluent. Such formulations may be solutions, dispersions or emulsions. These liquid compositions will also usually contain a surfactant to facilitate the azides penetration into the soil and generally enhance its effectiveness.

Nematocidal formulations of these azides may also contain stabilizers, spreading agents, fillers, other compatible pesticides and the like.

8 What is claimed is: 1. A compound of the formula:

a RNH(IJHO}C1 wherein X is halogen of atomic number 17 to 35 and R is z R l;-

wherein Z is a chalcogen atom of atomic number 8 to 16 and R is hydrogen; nonarylhydrocarbyl of l to 10 carbon atoms from the group consisting of alkyl, alkenyl, cycloalkyl and cycloalkenyl; nonarylhalohydrocarbyl from the group consisting of alkyl, alkenyl, cycloalkyl and cycloalkenyl and of 1 to 10 carbon atoms and 1 to 3 halogen atoms of atomic number 17 to 35; monocarbocyclicaryl from the group consisting of xylyl, cumyl, p-butylphenyl, p-octylphenyl, 2,4-dibutylphenyl and cinnamyl; substituted monocarbocyclicaryl of 6 to 15 carbon atoms, the benzene nucleus of said monocarbocyclicaryl radical being substituted with up to 3 alkoxy groups of 1 to 3 carbon atoms each, halogens of atomic number 17 to 35 or nitro groups; alkoxy of 1 to 6 carbon atoms; phenylthioalkyl in which the alkyl is of 1 to 3 carbon atoms and the phenyl is substituted with 0 to 2 halogen atoms of atomic number 17 to 35; or phenylsulfonylalkyl in which the alkyl is of 1 to 3 carbon atoms and the phenyl is substituted with 0 to 2 halogen atoms of atomic number 17 to 35.

2. The compound of claim 1 wherein Z is oxygen, X is chlorine and R is hydrogen.

3. Compound of claim 1 wherein X is chlorine and Z is oxygen.

4. Compound of claim 2 wherein R is hydrogen; alkyl of l to 6 carbon atoms; monoalkyl of 2 to 5 carbon atoms; cycloalkyl of 3 to 6 carbon atoms; substituted monocarbocylicaryl of 6 to 10 carbon atoms in which the benzene nucleus is substituted with up to 3 chlorine atoms, nitro groups or alkoxy groups of l to 2 carbon atoms each; chloroalkyl of 1 to 6 carbon atoms and 1 to 3 chlorine atoms; alkoxy of l to 3 carbon atoms; phenylthiomethyl in which the phenyl group is substituted With 0 to 3 chlorine atoms; or phenylsulfonylmethyl wherein the phenyl group is substituted with 0 to 3 chlorine atoms.

5. Compound of claim 3 wherein R is hydrogen, 4- chlorophenyl, 3,5 dimethoxyphenyl, 3,4,5 trimethoxyphenyl, t-butyl, cyclopropyl, 2,2-dichloroethyl, phenylthiomethyl, vinyl, 2-chloroethyl, 3,4-dichlorophenyl, 4- chloro-3-nitrophenyl, Z-chlorophenyl, 4-chlorophenylsulfonylmethyl, phenylsulfonylmethyl, 2 chloro 5 nitrophenyl, dichloromethyl, chloromethyl, 4-chlorophenylthiomethyl or isopropoxy.

References Cited Weygand et al., Chemische Berichte, vol. 99, pp. 1944, 1945, and 1955, (1966).

JOHN M. FORD, Primary Examiner US. Cl. X.R.

260-347.3, 332.2 C, 556 A, 558 S, 558 R, 558 D, 559 T, 559 R; 424226 

